Rate and Computational Studies for Pd-NHC-Catalyzed Amination with Primary Alkylamines and Secondary Anilines: Rationalizing Selectivity for Monoarylation versus Diarylation with NHC Ligands

Authors

Christopher Lombardi, York University
Richard P. Rucker, York University
Robert D.J. Froese, The Dow Chemical Company
Sepideh Sharif, York University
Pier Alexandre Champagne, New Jersey Institute of Technology
Michael G. Organ, York University

Document Type

Article

Publication Date

11-7-2019

Abstract

The relative rates of arylation of primary alkylamines with different Pd-NHC catalysts have been measured, as have the relative rates of arylation of the secondary aniline product in an attempt to understand the key ligand design features necessary to have high selectivity for the monoarylated amine product. As the substituents on the N-aryl ring of the NHC increase in size, selectivity for monoarylation increases and this is further enhanced by chlorinating the back of the NHC ring. Computations have been performed on the catalytic cycle of this transformation in order to understand the selectivity obtained with the different catalysts.

Identifier

85074055565 (Scopus)

Publication Title

Chemistry A European Journal

External Full Text Location

https://doi.org/10.1002/chem.201903362

e-ISSN

15213765

ISSN

09476539

PubMed ID

31593345

First Page

14223

Last Page

14229

Issue

62

Volume

25

Fund Ref

Eli Lilly and Company

Recommended Citation

Lombardi, Christopher; Rucker, Richard P.; Froese, Robert D.J.; Sharif, Sepideh; Champagne, Pier Alexandre; and Organ, Michael G., "Rate and Computational Studies for Pd-NHC-Catalyzed Amination with Primary Alkylamines and Secondary Anilines: Rationalizing Selectivity for Monoarylation versus Diarylation with NHC Ligands" (2019). Faculty Publications. 7200.
https://digitalcommons.njit.edu/fac_pubs/7200